Liquid crystal display device

ABSTRACT

A liquid crystal display device comprising a liquid crystal cell including a pair of substrates each having an alignment film on the surface thereof, and a liquid crystal filled in a space between the substrates, which is provided with a plurality of alignment regions, each region having the direction of alignment or the rise direction of liquid crystal molecule different from another region within a display region. The alignment film comprises a polyimide having a glass transition point of 300° to 400° C., a skeleton having no two-revolution axis, non-conjugated carbon occupying 10 to 60% of the total number of carbon excluding carbon atoms directly connected to imido group, a relative dielectric constant of 4 to 7 at a frequency of 1kH and at a temperature of 20° C., or an imidization degree of not less than 90%, or a polyimide obtained by reacting tetracarboxylic acid di-anhydride with a di-amine compound, or a polyimide obtained by imidizing a polyimide, the tetracarboxylic acid di-anhydride moiety being prohibited of the free rotation thereof.

This is a continuation of application Ser. No. 08/231,039 filed on Apr.22, 1994, allowed now U.S. Pat. No. 5,477,360.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a liquid crystal display device, and moreparticularly to a liquid crystal display device having a plurality ofregions different in alignment from each other.

2. Description of the Related Art

A liquid crystal display device is widely utilized as a display devicesuch as a wristwatch, an electronic calculator, and the like, since theliquid crystal display device is available as a thin device and can beoperated with a low electric voltage. There are known various types ofdisplay system, such as a twisted nematic (TN) type liquid crystaldisplay system, and a super-twisted nematic (STN) type liquid crystaldisplay system. With the TN type liquid crystal display system, it ispossible to produce a device having an excellent display characteristicwhich is comparable to that of CRT by incorporating therein an activeswitching element such as a thin film transistor (TFT). On the otherhand, with the STN type liquid crystal display system, it is possible toobtain a device which is capable of high duty multiplex driving.Therefore, the both systems are now much utilized as a display for aword processor or for a personal computer.

To be more specific, a liquid crystal display device of TN typecomprises a transparent substrate provided with a driving electrode, apicture element electrode and an alignment layer disposed on the surfacethereof for controlling the twist angle and tilt angle of liquid crystalmolecules, and a counter substrate provided with an alignment layer,which is positioned to face the above transparent substrate with anarrow space therebetween, thereby forming a liquid crystal cell. Aliquid crystal composition is enclosed between these substrates, and apair of polarizing plates are disposed as the outermost layers, thepolarizing direction of each plate being formed to cross each other.

However, the TN type liquid crystal display device is defective in thatsince alignment directions of the liquid crystal molecules take atwisted structure in the liquid crystal cell, and its manner of risefrom the substrate is accompanied with directionality, the color andcontrast ratio of the display varies according to the viewing direction,i.e. they are dependent on the visual angle. Moreover, the TN typeliquid crystal display device has drawbacks that the angle of visibilityof the display is narrow and light utilization efficiency is poor. Inparticular, since the manner of rise is accompanied with directionalityin the case of the TN type liquid crystal display device, there is nofundamental solution to the problem of the narrow angle of visibility.

The effect of directionality in rise of the liquid crystal moleculebecomes most prominent in the display of half-tone, so that thedirection which causes lowering of contrast and the direction whichcauses color inversion are directly determined according to thedirection of the rise.

To solve this problem, there is known a proposal wherein the directionof rise of liquid crystal molecules on an alignment film is variedwithin a picture element, thereby mutually compensating to each otherany differences in angle of visibility within the planar direction,thereby making the angle of visibility wider. In other words, a methodof changing the direction of rise of the liquid crystal molecule byforming a plurality of alignment films different in pre-tilt angle fromeach other has been proposed therein. However, when different kinds ofalignment films are combined, it would give rise to the generation of adirect current component even if the device is driven by an alternatingcurrent, thereby causing a drifting phenomenon of the optimum commonpotential to occur in an active-matrix drive, and also giving rise tothe occurrence of a defective display such as flicker and sticking.

There is another proposal to form a plurality of alignment regions,wherein the rise direction of liquid crystal molecule in each region isaltered from those in other regions. According to this proposal, analignment film is first subjected to a rubbing treatment, and thenoverlaid with a mask pattern through which the exposed portion of thealignment film is further subjected to rubbing treatment in a differentdirection from that of the previous rubbing treatment. However, thisproposal is also confirmed to cause undesirable phenomena, such as thedegradation of the alignment film and the lowering of alignmentproperty, due to the influences of various materials such as a solventcontained in a masking material, the masking material itself, adeveloper used for patterning the mask, and a stripping liquid used forremoving the mask. Moreover, there have been found other problems inthis method, such as peeling or shaving of the mask due to the poorrubbing resistance found in some kind of masking materials, thus makingthe selection of the masking material very difficult.

SUMMARY OF THE INVENTION

The object of this invention is to provide a liquid crystal displaydevice which is wide in effective angle of visibility, and free fromfault in display performance.

The liquid crystal display device of this invention is featured in thatthe direction of rise of liquid crystal molecule on an alignment film isvaried within a picture element, thereby mutually compensating to eachother any difference in angle of visibility within the planar directionthereby making the angle of visibility wider, wherein the partitioningof the alignment region is performed by repeating a plurality of timesthe alignment treatment using a mask, and the material for alignmentfilm as well as the masking material are suitably selected.

According to the first feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates, each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between the substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within a display pictureelement, wherein the alignment film comprises a polyimide having a glasstransition point of 300° to 400° C.

According to the second feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates, each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between the substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within a display pictureelement, wherein the alignment film comprises a polyimide whosemolecular skeleton is free from two-revolution symmetry axis.

According to the third feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates, each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between the substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within the displaypicture element, wherein the alignment film comprises a polyimide whosenon-conjugated carbon occupies 10 to 60% of the total number of carbonexcluding carbon atoms directly connected to imido group.

According to the fourth feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates, each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within a display pictureelement, wherein the alignment film comprises a polyimide whose relativedielectric constant is 4 to 7 at a frequency of 1 kH and at atemperature of 20° C.

According to the fifth feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between the substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within a display pictureelement, wherein the alignment film comprises a polyimide which isobtained by reacting tetracarboxylic acid di-anhydride with a di-aminecompound, or a polyimide which is obtained by imidizing the polymer, atetracarboxylic acid di-anhydride moiety of the polyimide being formedso as to prohibit the free rotation thereof.

According to the sixth feature of this invention, there is provided aliquid crystal display device comprising a liquid crystal cell includinga pair of substrates, each having an alignment film on the surfacethereof, and a liquid crystal filled in a space between the substrates,wherein the alignment film has a plurality of alignment regions, eachregion having a direction of alignment or a rise direction of liquidcrystal molecule different from another region within a display pictureelement, wherein the alignment film comprises a polyimide having animidization degree of not less than 90%.

According to the seventh feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a photosensitive resinhaving a modulus in tension of 20-500 kgf/mm².

According to the eighth feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a photosensitive resinhaving a photosensitivity to frequency of 300 nm.

According to the ninth feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a water-soluble polymer.

According to the tenth feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a photosensitive polymerhaving a thermal deformation temperature of 50° C. or more.

According to the eleventh feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a photosensitive resinhaving a modulus of elasticity in flexure of 0.9-5.1 GPa.

According to the twelfth feature of this invention, there is provided amethod of manufacturing a liquid crystal display device, which comprisesthe steps of forming an alignment film on a surface of each of a pair ofliquid crystal substrates, subjecting the alignment film to an alignmenttreatment in a first direction, selectively covering the alignment filmwith a mask pattern, and subjecting exposed portions of the alignmentfilm to an alignment treatment through the mask pattern in a seconddirection which is directionally different from the first direction,thereby providing a plurality of alignment regions, each region having adirection of alignment or a rise direction of liquid crystal moleculedifferent from another region within a display picture element, the maskpattern being formed of a material comprising a photosensitive resinhaving a Rockwell hardness of not less than M50.

According to the thirteenth feature of this invention, there is provideda method of manufacturing a liquid crystal display device, whichcomprises the steps of forming an alignment film on a surface of each ofa pair of liquid crystal substrates, subjecting the alignment film to analignment treatment in a first direction, coating a photosensitive resinon the alignment film, performing a developing process by using adeveloper thereby forming a mask pattern so as to selectively cover thealignment film, subjecting exposed portions of the alignment film to analignment treatment through the mask pattern in a second direction whichis directionally different from the first direction, thereby providing aplurality of alignment regions, each region having a direction ofalignment or a rise direction of liquid crystal molecule different fromanother region within a display picture element, and removing the maskpattern by using a stripping agent, the developer and/or stripping agentbeing formed of a material comprising an organic aqueous solution havinga boiling point of not more than 130° C.

According to the fourteenth feature of this invention, there is provideda method of manufacturing a liquid crystal display device, whichcomprises the steps of forming an alignment film on a surface of each ofa pair of liquid crystal substrates, subjecting the alignment film to analignment treatment in a first direction, coating a photosensitive resinon the alignment film, performing a developing process by using adeveloper thereby forming a mask pattern so as to selectively cover thealignment film, removing the developer by using a rinsing liquid,subjecting exposed portions of the alignment film to an alignmenttreatment through the mask pattern in a second direction which isdirectionally different from the first direction, thereby providing aplurality of alignment regions, each region having a direction ofalignment or a rise direction of liquid crystal molecule different fromanother region within a display picture element, and removing the maskpattern by using a stripping agent, the developer and/or stripping agentbeing formed of a material comprising an organic solvent having asolubility parameter of less than 8.9 cal^(1/2) ·cm^(-3/2), or more than10,0 cal^(1/2) ·cm^(-3/2).

Additional objects and advantages of the invention will be set forth inthe description which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and obtained by means ofthe instrumentalities and combinations particularly pointed out in theappended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of the specification, illustrate presently preferred embodiments ofthe invention, and together with the general description given above andthe detailed description of the preferred embodiments given below, serveto explain the principles of the invention.

FIG. 1 is a graph showing a relationship between the glass transitiontemperature of a polyimide constituting an alignment film of a liquidcrystal display device of this invention and changes in order parameterof alignment;

FIG. 2 is a graph showing a relationship between the ratio ofnon-conjugated carbon of a polyimide constituting an alignment film of aliquid crystal display device of this invention and changes in orderparameter of alignment;

FIG. 3 is a graph showing a relationship between the relative dielectricconstant of a polyimide constituting an alignment film of a liquidcrystal display device of this invention and changes in order parameterof alignment;

FIG. 4 is a graph showing a relationship between the magnitude ofexposure of an alignment film of a liquid crystal device of thisinvention to ultraviolet light and changes in order parameter ofalignment;

FIG. 5 is a graph showing the solubility of PVA constituting the maskingmaterial employed in the manufacture of a liquid crystal device of thisinvention;

FIG. 6 is a graph showing a relationship between the heat resistancetemperature of a photoresist constituting the masking material employedin the manufacture of a liquid crystal device of this invention and theratio of occurrence of defective product due to the deformation of thephotoresist;

FIG. 7 is a graph showing a relationship between the modulus ofelasticity in flexure of a photoresist constituting the masking materialemployed in the manufacture of a liquid crystal device of this inventionand the ratio of occurrence of defective product due to the deformationof the photoresist;

FIG. 8 is a graph showing a relationship between the Rockwell hardnessof a photoresist constituting the masking material employed in themanufacture of a liquid crystal device of this invention and the ratioof occurrence of defective product due to the deformation of thephotoresist;

FIG. 9 is a graph showing a relationship between the boiling point of anorganic material constituting the developer employed in the manufactureof a liquid crystal device of this invention and a voltage-retainingrate;

FIG. 10 is a graph showing a relationship between the pH of a developeremployed in the manufacture of a liquid crystal device of this inventionand a contrast ratio;

FIG. 11 is a graph showing a relationship between the solubilityparameter of a developer employed in the manufacture of a liquid crystaldevice of this invention and a pretilt angle of a liquid crystalmolecule;

FIG. 12 is a sectional view of a liquid crystal device representing oneembodiment of this invention;

FIGS. 13A to 13E are sectional views explaining the manufacturingprocess of a liquid crystal device representing one embodiment of thisinvention;

FIG. 14 is a diagram showing a uniform contrast, which was free from thedependency on the viewing angle according to one embodiment of a liquidcrystal device of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present inventors have found after repeated researches andexperiments for selecting suitable masking materials and alignment filmmaterials that the following specific polyimide-based alignment filmmaterial and resist mask materials are found to be useful.

1. The present inventors have found after a repeated study on the resistmask materials and polyimide-based alignment film materials that thereis a definite relationship between the thermal characteristic ofpolyimide-based alignment film materials and a solvent to be used forpatterning a resist mask.

Namely, it has been found that a butadiene cyclized rubber-based resistas a negative resist, and an acrylic resist as a positive resist havebeen found suitable as masking materials in view of their excellentcharacteristics such as good patterning performance, and highresistivity to the peeling and shaving during a rubbing alignmenttreatment.

Since a butadiene cyclized rubber-based material and acrylic materialare excellent in elasticity, it is free from the problems of peeling andshaving as mentioned above.

For the butadiene cyclized rubber-based material, alkylbenzene can beused as a solvent, and at the same time the development treatment can beperformed using alkylbenzene as a developing agent. For peeling orstripping a mask, an aromatic acidic solvent such asalkylhydroxybenzene, alkylbenzene sulfonate can be used.

For the acrylic material, cellosolve series material can be used as asolvent, and the development treatment can be performed using alkaliaqueous solution as a developing agent. For peeling or stripping a mask,cellosolve series material can be used.

The present inventors have found after studying various polyimides forusing them as an alignment film material which is completely insolubleto and free from any influence of this kind of organic solvent, that awhole aromatic polyimide (polyimide in which the skeleton consists ofaromatic groups) having a glass transition point of 450° C. issusceptible to the influence of above solvent, but a polyimidecontaining an aliphatic straight chain and having a glass transitionpoint of 380° C. is hardly susceptible to the influence of abovesolvent.

When the degree of influence by the solvent was examined in relative tothe change in glass transition temperature, the results as shown in FIG.1 were obtained. The data shown in FIG. 1 were taken by first immersinga portion of an alignment film treated in advance with rubbing as arepresentative example into a negative-resist-stripping agent for onehour, and then forming a liquid crystal cell into which a liquid crystalwas filled, and finally measuring the ratio of order degree of alignmentof an immersed portion to the order degree of alignment of non-immersedportion.

It would be clear from the data shown in FIG. 1 that a polyimide havinga lower glass transition point is less susceptible to the influence ofthe solvent mentioned above. This phenomena can be attributed to theinfluence of skeletal structure of polyimide and internal structure ofmolded form of polyimide to its glass transition temperature. However,it has been found that when the glass transition temperature thereof isless than 300°, it will cause the lowering of the alignment stability innormal state after being kept for 100 hours at 80° C. The degree oflowering of the alignment degree of alignment after a life test inrelative to the initial alignment also indicated almost the same trendsas the results shown in FIG. 1.

As is clear from the above results, the structure of polyimide alignmentfilm has an important influence to the resist mask material. Inpractical viewpoint, when a polyimide having a glass transitiontemperature of 300 to 400° C., preferably 350° to 400° C. reflecting itschemical structure is used, it is possible to perform a treatment ofpicture element partition alignment by repeating several times therubbing treatment of the same alignment film using a mask withoutcausing the degradation of alignment. Meanwhile, when a positive resistis used as a mask material, the polyimide may be applied to an organicalkali aqueous solution having a low alkali concentration.

2. The present inventors have found that there is a definiterelationship between the skeleton of polyimide constituting an alignmentfilm and a solvent to be used for patterning a resist mask.

The present inventors have found after studying various polyimides forusing them as an alignment film material which is completely insolubleto and free from any influence of this kind of organic solvent, that apolyimide having a skeleton of straight chain is susceptible to theinfluence of above solvent, but a polyimide containing an alicyclic oran aliphatic side chain is hardly susceptible to the influence of abovesolvent. Namely, the influence of solvent differs according to theflexibility of the skeleton of polyimide.

The solvent to be used for the resist mentioned above is mainly ofaromatic type, and low in polarity, so that when the skeleton thereof isinflexible and includes the polar groups which are not to be protrudedout of the surface of the film, the solvent is easily impregnated intothe chain so as to weaken the effect of the alignment treatment. Inparticular, a polyimide having two-revolution symmetry axis, but beingsoluble to the solvent contains a bulky side chain so as to be solubleto the solvent. With this kind of skeleton, the distance between thechains becomes enlarged in the chain structure of the film after beingformed into a film, so that the solvent is more easily penetrated intothe film, thus causing prominent degradation of alignment.

3. The present inventors have found that there is a definiterelationship between the skeleton of polyimide constituting an alignmentfilm and a solvent to be used for patterning a resist mask.

The present inventors have found, after studying various polyimides forusing them as an alignment film material which are completely insolubleto and free from any influence of this kind of solvent, that a polyimidehaving a whole aromatic skeleton is susceptible to the influence ofabove solvent, and a polyimide having an alicyclic or aliphatic sidechain is hardly susceptible to the influence of above solvent.

When the degree of the influence was investigated by changing the ratioof non-conjugated carbon to the total number of carbon except thosedirectly connected to imido group in the skeletal structure ofpolyimide, the results as shown in FIG. 2 were obtained. An example ofcalculation representing the ratio of nonconjugated carbon to the totalnumber of carbon when a typical polyimide the following chemical formula(1) is used is shown herein. ##STR1## wherein n is polymerizationdegree.

In this polyimide having the chemical formula (1), the number of carbonhaving no π electron such as benzene ring and not belonging toconjugated carbon is 4 among the total number of carbon, i.e. 29 perrepeating unit excepting the carbon atoms directly connected to imidogroup. Therefore, in this case, the ratio occupied by the non-conjugatedcarbon is 13.8%.

The data shown in FIG. 2 were taken by first immersing a portion of analignment film treated in advance with rubbing into a resist-strippingagent for one hour, and then forming a liquid crystal cell into which aliquid crystal was filled, and finally measuring the ratio of orderdegree of alignment of an immersed portion to the order degree ofalignment of non-immersed portion. As is clear from the results shown inFIG. 2, a better result could be obtained when a polyimide having alarger ratio of non-conjugated is used. However, it has been found thatwhen this ratio is exceeded over 50%, it will cause the lowering of thealignment stability in normal state after being kept for 100 hours at80° C. The degree of lowering of the alignment degree of alignment aftera life test in relative to the initial alignment also indicated almostthe same trends as the results shown in FIG. 2.

As is clear from the above results, the skeleton composition ofpolyimide alignment film has an important influence to the resist maskmaterial. In practical viewpoint, when a polyimide having non-conjugatedcarbon occupying 10 to 60%, preferably 20 to 45% among the total numberof carbon excluding the carbons directly connected to imido group isused, it is possible to perform a treatment of picture element partitionalignment by repeating several times the rubbing treatment to the samealignment film by using a mask without causing the degradation ofalignment.

4. The present inventors have found that there is a definiterelationship between the electric characteristics of polyimideconstituting an alignment film and a solvent to be used for patterning aresist mask.

The present inventors have found, after studying various polyimides foruse as an alignment film material, which are completely insoluble to andfree from any influence of this kind of solvent, that a whole aromaticpolyimide having a relative dielectric constant of 3.5 under theconditions of 1 kHz in frequency at 20° C. is susceptible to theinfluence of above solvent, whereas a polyimide with an aliphaticstraight chain having a relative dielectric constant of 4.2 is hardlysusceptible to the influence of above solvent.

When the degree of the influence was investigated by changing therelative dielectric constant under 1 kHz, the results as shown in FIG. 3were obtained.

The data shown in FIG. 3 were taken by first immersing a portion of analignment film treated in advance with rubbing into a resist-strippingagent for one hour, and then forming a liquid crystal cell into which aliquid crystal was filled, and finally measuring the ratio of orderdegree of alignment of an immersed portion to the order degree ofalignment of non-immersed portion.

As is clear from the results shown in FIG. 3, a polyimide having alarger relative dielectric constant is less susceptible to the influenceof the solvent mentioned above. These results may be attributed to thefact that the value of relative dielectric constant reflects theskeletal structure and the inner structure of a film of a polyimide.However, it has been found that when the relative dielectric constant isexceeded over 6, it will cause the lowering of the alignment stabilityin normal state after being kept for 100 hours at 80° C. The degree oflowering of the alignment degree of alignment after a life test inrelative to the initial alignment also indicated almost the same trendas the results shown in FIG. 3.

As is clear from the above results, the structure of polyimide alignmentfilm has an important influence to the resist mask material. Inpractical viewpoint, when a polyimide having a relative dielectricconstant of 4 to 7, preferably 4.5 to 6.5 reflecting the structure ofpolyimide is used, it is possible to perform a treatment of pictureelement partition alignment by repeating several times the rubbingtreatment to the same alignment film by using a mask without causing thedegradation of alignment.

5. The present inventors have found that there is a definiterelationship between the skeleton of polyimide constituting an alignmentfilm and a solvent to be used for patterning a resist mask.

The present inventors have found, after studying various polyimides forusing them as an alignment film material which is completely insolubleto and free from any influence of the solvent, developer, rinsing liquidand stripping liquid for the photoresist constituting a maskingmaterial, and the rinsing liquid to be used after stripping agent, thata polyimide which is obtained by reacting tetracarboxylic aciddi-anhydride with a di-amine compound, and/or a polyimide which isobtained by imidizing the polymer obtained by reacting tetracarboxylicacid di-anhydride with a di-amine compound are susceptible to theinfluence of above mentioned solvent if the tetracarboxylic aciddi-anhydride moiety thereof is made rotatable, but are hardlysusceptible to the influence of above mentioned solvent if thetetracarboxylic acid di-anhydride moiety thereof is not made rotatable.

The examples of a polyimide having a tetracarboxylic acid di-anhydridemoiety thereof, which are made fee to rotate are polyimide moleculeshaving a single bond as shown in the following general formula (2)wherein R connected to a pair of imido groups is --CH₂ --, --CH₂ --CH₂--, --CO--, --CH₂ --CO--CH₂ --, --CH₂ --COO--, CF₂ ##STR2##

As examples of a polyimide having a tetracarboxylic acid di-anhydridemoiety thereof, which are made free to rotate, the following compoundsrepresented by the general formula (3) and (4) may be mentioned.##STR3##

On the other hand, the examples of a polyimide having a tetracarboxylicacid di-anhydride moiety thereof, which are made unrotatable arepolyimide molecules wherein R in the above general formula (2) is ofcyclic structure, such as cyclobutane ring, benzene ring, cyclohexane,or includes a double bond, triple bond such as --CH═CH--,--C.tbd.C--

As examples of a polyimide having a tetracarboxylic acid di-anhydridemoiety thereof, which are made unrotatable, the following compoundsrepresented by the general formula (5) (6) and (7) may be mentioned.##STR4##

The fact that whether or not the tetracarboxylic acid di-anhydridemoiety is possible to rotate has much to do with the influence of abovesolvent means that the degree of influence to be effected by the solventdiffers according to the flexibility of the skeleton of polyimide. Thereason for this difference in degree of influence by the solvent may beexplained as follows.

The skeleton of polyimide whose tetracarboxylic acid di-anhydride moietyis made free to rotate is high in flexibility so that the space betweenpolyimide molecular chains is rather wide, thereby easily allowing thesolvent to be penetrated therein. When the solvent molecule ispenetrated into the polyimide molecule, the space between polyimidemolecular chains which have been aligned by the rubbing treatment isexpanded, thereby giving rise to the relaxation (randomization) of thealigned molecule chains. When the aligned molecule chains arerandomized, the effect of rubbing treatment as well as the alignmentdegree of the liquid crystal within a liquid crystal cell are lowered,thereby causing a defective alignment.

By contrast, in the polyimide whose tetracarboxylic acid di-anhydridemoiety is made unrotatable, the space between polyimide molecular chainsis rather dense (in most case, in the state of laminar structure), sothat the solvent can hardly be penetrated into the polyimide moleculechains. Accordingly, the relaxation of the polyimide molecule chainswould not occur, and therefore any defective alignment would not becaused.

6. The present inventors have found that there is a definiterelationship between the imidization degree of polyimide constituting analignment film and a solvent to be used for patterning a resist mask.

Polyimide alignment film is generally formed by first reacting an aciddi-anhidride or the derivative thereof with a diamine usually in anon-proton type polar solvent, thereby producing a polyamide acidsolution, and then the polyamide acid solution is coated on a substrateto be dehydrated and closed of its ring as indicated in the followingreaction formula. ##STR5## wherein R₁ and R₂ are divalent organic group,and n represents polymerization degree.

When polyamide acid moiety is existed in the polyimide alignment filmdue to an insufficient imidization, the N--H bond of the polyamide acidmoiety tends to be transformed upon contact with an acid or an alkali.Generally, in the case of a positive resist, a developer to be used isalkaline, whereas in the case of negative resist, a developer to be usedis acidic. Therefore, when a polyimide alignment film containing thereina large amount of polyamic acid moiety due to an insufficientimidization is contacted with a developer or stripping liquid, it willcause the N--H bond to react with the developer or stripping liquid,thereby inviting the denaturing of the polyamic acid moiety, and thedegradation of the alignment film. As a result, the alignment of theliquid crystal becomes non-uniform, thus lowering the display quality.

The present inventors have found after studying various polyimides foruse as an alignment film material, which are completely insoluble to andfree from any influence of this kind of solvent, that it is possible tosolve the above problems by using, as an alignment film, a polyimidehaving an imidization degree of not less than 90%, preferably not lessthan 95%.

This polyimide film is preferably made from a polyimide containing atthe ratio of not less than 90% a polyimide moiety represented by thefollowing formula (9). In this case, it is preferable to use as amasking material a negative resist comprising cyclized rubber addedtherewith a bisazido compound. ##STR6##

A polyimide alignment film to be employed according to this invention isgenerally formed by first reacting an acid di-anhydride or thederivative thereof with a diamine usually in a non-proton type polarsolvent, thereby producing a polyamide acid solution, which is thendehydrated and closed of its ring. It is also possible to obtain thepolyimide alignment film by reacting an acid di-anhydride or thederivative thereof with a diisocyanate usually in a non-proton typepolar solvent. The polyamide film or polyimide is useful in thisinvention as far as the intrinsic viscosity thereof (as measured at 30°C., in dimethylformaldehyde 0.05 g/dl) is not less than 0.05 g/dl,preferably in the range of 0.05 to 5 g/dl.

Examples of acid di-anhydride or the derivative thereof to be used forobtaining the above polyimide are alicyclic tetracarboxylic aciddi-anhydride or derivatives thereof such as 2,3,5-tricarboxycyclopentylacetic acid di-anhydride, cyclobutane tetracarboxylic acid di-anhydride,cyclopentane tetracarboxylic acid di-anhydride,5-(2,5-dioxotetrahydrofuryl)-3-methylcyclohexene dicarboxylic aciddi-anhydride, bicyclo(2,2,2)-octo-7-ene-2,3,5,6-tetracarboxylic aciddi-anhydride,3,5,6-tricarboxynorborane-2-acetic acid dianhydride;alicyclic tetracarboxylic acid di-anhydride or derivatives thereof suchas 1,2,3,4-butane tetracarboxylic acid di-anhydride, 2,2,6,6-heptanetetracarboxylic acid di-anhydride; aromatic tetracarboxylic aciddi-anhydride or derivatives thereof such as pyromellitic aciddi-anhydride,3,4,3',4'-benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid di-anhydride, naphthalene tetracarboxylic aciddi-anhydride, bis(dicarboxyphenyl)propane di-anhydride,bis(dicarboxyphenyl)sulfone di-anhydride, bis(dicarboxyphenyl)etherdi-anhydride, 3,4,3',4'-dimethylphenylsilane tetracarboxylic acid,perfluoroisopropylidene tetracarboxylic acid di-anhydride. Thesecompounds may be used individually or in combination.

Among these compounds, 2,3,5-tricarboxycyclopentyl acetic aciddi-anhydride, or derivatives thereof are preferable as these compoundsare excellent in solubility, so that a polyimide solution which issuited for a low temperature treatment can be obtained.

Examples of diamine to be useful in this invention are aliphatic oralicyclic diamines such as ethylene diamine, propylene diamine,tetramethylene diamine, pentamethylene diamine, hexamethylene diamine,heptamethylene diamine, octamethylene diamine, nonamethylene diamine,4,4'-dimethylheptamethylene diamine, 1,4-diaminocyclohexane,tetrahydrodicyclopentadienylene diamine, hexahydro-4,7-methanoindanylenedimethylene diamine; aromatic diamines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,6-diaminotoluylene,2,4-diaminotoluylene, paraphenylene diamine, methaphenylene diamine,paraxylene diamine, methaxylene diamine, 4,4'-diaminodiphenyl sulfone,3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide,4,4'-diaminobenzophenone, 2,6-diaminonaphthalene,1,5-diaminonaphthalene, 4,4'-diaminodiphenyl,3,3'-dimethyl-4,4'-diaminophenyl methane,3,3'-dicarboxy-4,4'-diaminodiphenyl methane, and3,3'-dimethyl-4,4'-diaminodiphenyl methane; and diaminoorganosiloxanerepresented by the following general formula (10). These compounds maybe used individually or in combination. ##STR7## wherein R₃ is methylenegroup containing 1 to 50 carbon atoms, phenyl ring, or cyclohexane ring;R₄ is alkylene group containing 1 to 20 carbon atoms, phenyl group, orcyclohexyl group; and m is an integer of 1 to 100.

As a diisocyanate, a diamine whose amino group is substituted byisocyanate group can be used.

As a reaction solvent to be used for the reaction between the above aciddianhydride or the derivative thereof and diamine or diisocyanate,non-protonic polar solvent such as dimethyl amide, dimethyl acetoamide,dimethyl sulfoxide, hexamethyl phosphoric amide, N-methyl-2-pyrrolidone,tetramethyl urea, or gammabutyrolactone may be used individually or incombination. It is also possible to mix an ordinary organic solvent suchas alcohol, ketone, ester, or hydrocarbon into the above reactionsolvent.

Since the polyimide to be used in this invention has an imidizationdegree of not less than 90%, the amount of N--H bond existing in thepolyamide acid moiety is few, so that it is possible to inhibit thedegradation of the surface of the alignment film during the developingand stripping processes of a resist material. The imidization degree isherein defined as the ratio of polyimide (II) component to the totalamount of polyamide acid (I) component and polyimide (II) component, orthe ratio of polyimide (II) component to the whole components. Thisimidization degree can be easily determined by for example measuring achange in infrared absorption spectrum of carbonyl group of imido ringof polyimide (II), which is generated as the polyamide acid (I) isdehydrated and transformed into a closed ring.

As a method of increasing the imidization degree up to over 90%, eithera method of employing an organic solvent-soluble polyimide, or theconventional method of thermally or chemically dehydrating a coatedlayer of polyamic acid to form a ring closure thereby transforming itinto polyimide can be adopted. An N--H bond of polyamic acid moietyexisting in the aligned layer of polyimide film tends to react throughan acid-salt reaction with alkylbenzenesulfonic acid constituting acidiccomponent of the resist stripping solution. As a result, the alignmentlayer of a polyimide film containing polyamic acid component is badlyaffected, causing the disturbance of the main chain constituting thealignment film aligned in advance by the rubbing direction, therebymaking the alignment of the liquid crystal ununiform.

However, according to this invention, the alignment layer of a polyimidefilm contains the polyamic acid component as little as less than 10%, itis possible to prevent the quality of display of a liquid crystal devicefrom being degraded during the process of the development or strippingof the resist material. As a result, it is possible to obtain a highquality display device having a uniform angle of visibility even if itis viewed from any direction.

According to this invention, a polyimide containing not less than 90% ofpolyimide moiety represented by the general formula (8) is preferablyemployed as a polyimide film. This polyimide is excellent in solubility,so that it can be easily dissolved in the state of polyimide into anorganic solvent such as gammabutyrolactone, thereby forming a stablesolution. Therefore, this polyimide can be easily coated over asubstrate to be formed into a completely imidized polyimide film on thesubstrate by heating it at such a relatively low temperature of 180° C.that would not destroy other members such as a color filter.

When a negative resist comprising a cyclized rubber added with abisazido compound is used as a resist in the alignment treatment ofpolyimide film having an imidization degree of not less than 90%, it ispossible to easily form such a fine pattern of several microns. This isdue to the fact that the negative resist comprising a cyclized rubberadded with a bisazido compound is highly sensitive to the irradiation ofultraviolet ray so as to cause the cross-linking reaction of the resist.Moreover, since this resist is as hard as the polyimide film, theproblems such as the scratching of the surface of the alignment film bythe peeled or removed pieces from the surface of the resist during therubbing alignment treatment or the spoiling of the clean room by thepeeled or removed pieces from the resist can be avoided.

Even though either of a negative photoresist or a positive photoresistmay be used, it is preferable to use the negative photoresist. When apositive photoresist is to be employed, it is preferable to use anacryl-based positive photoresist as explained below.

In the manufacture of semiconductor device, a novolak resin is widelyutilized as a base resin of a positive resist. However, since thenovolak resin is poor in elasticity, the use of novolak type positiveresist would cause the generation of peeled or removed products from thesurface of the resist during the second rubbing treatment, therebygiving rise to the scratching of the surface of the aligned film, or adefective display resulting from the dust (peeled products).

By contrast, when a positive resist comprising acryl resin as a baseresin is used, the generation of peeled or removed products from thesurface of the resist can be avoided, and an excellent result asobtainable in the case of butadiene cyclized rubber-based negativeresist would be obtained. The reason for this can be explained that theacryl resin is rather elastic as compared with the novolak resin, and isexcellent in adhesivity to the under layer of polyimide alignment film.

When an acryl-based positive resist of chemically magnified type whichis highly sensitive is employed among others, it is possible to obtain afine pattern of submicron. This chemically magnified resist is a mixturecomprising a base resin such as acryl resin or polymethacrylate, anacid-generating agent such as onium salt, nitrobenzene ester, orsulfonate, and a solubility inhibiting agent such as acetal compound,polyphthal aldehyde, cylyl ether polymer, aliphatic acid ester ormethoxymethyl melamine.

As mentioned hereinabove, when a polyimide having an imidization degreeof not less than 90% is employed as an alignment film, an excellentresult can be obtained. However, it is also possible to employ apolyimide having an imidization degree of less than 90%, provided that apositive resist is to be employed. When a polyimide having animidization degree of less than 90% is employed, problems such asdeterioration of display quality resulting from peeled or removedproducts from the surface of the positive resist can be avoided asexplained below.

It has been found that in the process of forming a positive resistpattern by means of picture element partition alignment treatment, analkaline developing agent is contacted with the surface of the alignmentfilm, thereby causing the denaturing of the surface of the alignmentfilm, and lowering the pretilt angle of a liquid crystal molecule.However, when a polyimide having an imidization degree of less than 90%is employed, the polyamic acid included in the alignment film functionsto raise the pretilt angle, thereby allowing a suitable pretilt angle(2° to 10°) to be obtained. As a result, it is possible to obtain a highquality display device being excellent in liquid crystal alignment, andhaving a uniform angle of visibility even if it is viewed from anydirection.

In this case, a cresol novolak-based or acrylic positive resist can beemployed as a resist material. This resist is highly sensitive to a UVray having a frequency of 365 nm or 406 nm, and allows a fine pattern ofseveral microns to be formed.

7. The present inventors have found after various experiments that amask material having a modulus in tension of 20 to 500 kgf/mm²,preferably 100 to 400 kg/mm² is suitably employed to obtain an excellentresult.

In view of requirements for the patterning process, a photoresistmaterial, in particular a cresol novolak-based positive resist which hasbeen widely used can be employed. This resist contains a sensitizingagent whose structure is transformed upon the irradiation of UV ray soas to cause the cresol novolak-based positive resist to show theinherent solubility of the cresol novolak. Accordingly, the molecularweight thereof is controlled so as to be easily dissolved into water.

Phenol resin-based resist is featured in that it is fragile, and poor inmechanical shock. Generally, a hard resin is low in elasticity modulus,and do not have a yield point from which a plastic deformation isinitiated. When a rubbing treatment is conducted on this resist, theportions to which fibers of cloth have been contacted are liable to beshaved thereby generating shavings. The shavings thus generated not onlybecome a cause of dusty materials, but also adhere to the rubbing cloththereby spoiling the substrate and extremely lowering the effects of therubbing treatment.

Accordingly, it is required for a masking material to have apredetermined elasticity. It has been found by the present inventorsafter great deal of study on various high molecular materials that whena material having a modulus of elasticity in tension of not less than 20kgf/mm² is employed, the phenomena of peeling and shaving of the filmcan be avoided as shown in the following Table 1. As for the influenceto the alignment of the masking material, it has been found that when amaterial having a modulus of elasticity in tension of more than 500kgf/mm² is employed, it gives rise to not only the blur of an alignmentpattern due to the deformation of the mask, but also a lot of the maskbeing left unremoved.

                  TABLE 1                                                         ______________________________________                                                    Modulus of                                                                    Elasticity                                                        Mask        in Tenson    Peeling. Blur of                                     Materials   (kqf/mm.sup.2)                                                                             Shaving  Pattern                                     ______________________________________                                        Cured Rubber                                                                              100          None     None                                        Nylon 66    220          None     None                                        Nylon 6     120          None     None                                        Polystyrene 300          None     None                                        PVA         150          None     None                                        Polyurethane                                                                              600          None     Admitted                                    Polyethylene                                                                              850          None     Admitted                                    Phenol       8           Admitted None                                        Polyester    15          Admitted None                                        ______________________________________                                    

Therefore, it has been confirmed that, by using, as a masking material,a material having a modulus of elasticity in tension ranging from 20 to500 kgf/mm², it is possible to perform a patterning of a resist withoutcausing the lowering of the effects of alignment treatment, therebyrealizing in an industrial scale the partition alignment of pictureelements.

8. The present inventors have found after various experiments that amask material having a photosensitivity to wave-length of not less than300 nm can be suitably employed to obtain an excellent result. As iswell known, the selection of masking materials is very difficult, assome of masking materials are found to be poor in rubbing resistance sothat it give rise to the problems such as peeling and shaving of mask.In view of these problems, the present inventor have conducted the studyon various materials to find that some kinds of conditions, which arenot expected up to date, are required for the masking material to beuseful as explained below.

Since the masking material is used for partitioning the alignmentregion, a patterning thereof is required. In this case, in order torealize a precise patterning in micron order, it is most preferable toemploy a photoresist in the pattering process. In this patterningprocess, an electromagnetic wave of short wavelength of such as i beam,g beam, electron beam, exma laser beam or X-ray is irradiated onto thephotoresist through a photomask. It has been found in this case thatwhen a beam having a wavelength shorter than that of the g beam, or abeam having a wavelength of less than 300 nm is irradiated onto analignment film processed in advance with a rubbing alignment treatment,the effect of the alignment treatment performed in advance is decreasedaccording to the magnitude of the irradiation dose.

FIG. 4 indicates changes in the order degree of the alignment, whereinthe liquid crystal cell was produced by first rubbing the alignment filmof a thermally ring-closed polyimide, and then irradiating a beam250-300 nm in wavelength onto the aligned film by changing theirradiation dose. These changes in the order degree of the alignment canbe said to be a phenomenon that can be brought about when a portion ofthe skeleton of the alignment film is cut off upon absorption therein ofthe beam of this range of wave-length. The beam having a wave-length of250 nm has an energy of 114 kcal/mol, which is sufficient for cuttingthe ordinary carbon-carbon bond. Therefore, when the resist itself isemployed as a rubbing mask, or even when the photoresist is employed forpatterning the masking material, the use of a beam having a wave-lengthof less than 300 nm is not desirable.

Therefore, it has been realized by using, as a masking material, amaterial having a photosensitivity to wave-length of not less than 300nm to perform a patterning of a resist without lowering the effects ofalignment treatment, thereby realizing the partition alignment ofpicture elements.

9. The present inventors have found after various experiments that whena water-soluble polymer is employed as a mask material, it is possibleto obtain an excellent result.

Namely, it has been confirmed by the present inventors that awater-soluble polymer such as polyvinyl alcohol is useful as a maskmaterial which is excellent in rubbing resistance, and does not give abad influence to the alignment film made of for example polyimide. Withthe use of a water-soluble polymer, it is possible to perform thepatterning and stripping of the resist without requiring a solvent whichmay dissolve the alignment film material, such as polyimide. Thewater-soluble polymer also has a sufficient rubbing resistance to beused as a masking material for an alignment film.

However, since the water-soluble polymer such as polyvinyl alcoholitself is not suited for being formed into a pattern, it is required toutilize a photoresist for forming a pattern. It has been confirmed thatwhen a photoresist material to be developed with a positive or negativestrong alkaline aqueous solution is used, the patterned portion isdissolved due to the use of the aqueous polymer during the developmentprocess, thereby allowing the alkaline developer to directly contactwith the alignment film to degrade the quality of alignment of thealignment film. Therefore, it is required for the water-soluble polymersuch as polyvinyl alcohol to be used as a mask for the alignment film toadjust the water-solubility thereof so as not to allow the alkalinedeveloper to contact with the alignment film.

It has been confirmed by the present inventors after repeated studiesthat the water-solubility of polyvinyl alcohol can be adjusted byadjusting the saponification degree, the polymerization degree andsintering temperature of the polyvinyl alcohol. To be more specific, apolyvinyl alcohol (PVA2) having 90% or more in saponification degree,1000 or more in polymerization degree and 120° C. or more in sinteringtemperature is found to be suitable as being low in water-solubilityunder the room temperature. By the way, PVA1 is a polyvinyl alcoholwhich does not meet the above conditions.

These conditions are required for the polyvinyl alcohol in thedevelopment using an alkaline aqueous solution. It has become possibleby the use of an aqueous polymer meeting these conditions to perform arepeated alignment treatment, by masking the alignment portion withoutconsidering the selection of an alignment film material.

Since an alignment film is exposed to a solvent having a high solubilityunder a high temperature, during the stripping process of a resist insubsequent to the second alignment treatment, the use of a negativeresist may become a cause of the deterioration of alignment. However,when a resist material is formed over a water-soluble polymer, theportion of water-soluble polymer would be easily dissolved uponimmersing the substrate into a hot water, thus allowing the resistportion to be easily stripped off. Therefore, it has become possible touse all kinds of resist by disposing thereon a water-soluble polymerlayer.

The alignment film to be used in this case may be the one whichcomprises a water-insoluble polymer film, whose surface has beensubjected to an alignment treatment by means of for example rubbingtreatment, or the one comprising a rhombic evaporated layer of aninorganic material such as SiO. As the water-insoluble polymer,polyimide, polyamide, polyamideimide, polysulfone, polyester,polybenzoimidasol, polyether, polysulfide, polybenzoimidazopyrroline,polyphenyl, polynaphthalene, polycyanoacetone,polyacrylonitrile,polystyrene, or polyaniline may be employed.

10. The present inventors have found after various experiments that whena photosensitive resin having a thermal deformation temperature of 50°C. or more, preferably 130° C. or more is employed as a mask material,it is possible to obtain an excellent result.

It has been found by the present inventors upon examining anethylene-base positive resist comprising polyethylene having aphotosensitive group bonded thereto, the resist is liable to bedenatured and deformed during the rubbing treatment. It has been furtherfound that the deformation of the resist is brought about by the thermaldisintegration of part of the resist due to the generation of africtional heat between the rubbing cloth and the resist during therubbing treatment.

When the resist is deformed, it is no more possible to preciselypartition the alignment region for obtaining a plurality of alignmentregions, wherein each region has a different rising direction of aliquid crystal molecule from that of other regions. Moreover, thedisintegrated portion of the resist resulted from the frictional heatmay cause the contamination of a clean room, or adhere to a rubbingcloth to lower the effect of rubbing treatment. Therefore, it isrequired for the masking material to have a suitable heat resistance.

It has been found by the present inventors upon examining variouspolymers that when a polymer having a heat resistance of 50° C. or moreis used, the deformation of the resist during the rubbing treatment canbe avoided as shown in FIG. 6.

Thus, with the use of photosensitive resins having a thermaltransformation temperature of 50° C. or more, preferably 130° C. ormore, it is possible to perform the patterning of the photosensitiveresin layer without spoiling the effects of the alignment, and to obtaina precise partition of picture element.

11. The present inventors have found after various experiments that amask material comprising a photosensitive resin having a modulus ofelasticity in flexure of 0.9 to 5.1 GPa, preferably 2.0 to 4.0 GPa isemployed, it is possible to obtain an excellent result.

In view of requirement for the patterning, a photoresist material, inparticular a cresol novolak-based positive resist has been widely used.When this cresol novolak-based positive resist was utilized by thepresent inventors, it was found that part of the resist was shavedduring the rubbing treatment, thereby producing shavings. The shavingsthus produced not only become a cause of contamination of the cleanroom, but also adhere to the rubbing cloth thereby spoiling thesubstrate and extremely lowering the effects of the rubbing treatment.This cresol novolak-based positive resist belongs to phenol resin, andtherefore is fragile and poor in resistance to mechanical shock justlike phenol resin. Accordingly, it is required for a masking material tohave a predetermined elasticity.

It has been found by the present inventors after great deal of study onvarious high molecular materials that when a material having a modulusof elasticity in flexure of not more than 5.1 GPa is employed, thephenomena of peeling and shaving of the film can be avoided as shown inthe following Table 7. On the hand, when a material having a modulus ofelasticity in flexure of 0.9 GPa is employed, it gives rise to not onlythe deformation of the mask thereby making it impossible to perform aprecise partition of the alignment region, but also a lot of the maskbeing left unremoved.

Thus, with the use of a photosensitive resin having a modulus ofelasticity in flexure of 0.9 to 5.1 GPa as a masking material, it ispossible to perform the patterning of the photosensitive resin layerwithout spoiling the effects of the alignment, and to obtain a precisepartition of picture element.

12. The present inventors have found after various experiments on themasking materials that a mask material comprising a photosensitive resinhaving a Rockwell hardness of M50 or more, preferably M70 or more isemployed, it is possible to obtain an excellent result.

When a cresol novolak-based positive resist was utilized as a mask bythe present inventors, it was found that part of the resist was shavedduring the rubbing treatment, thereby producing shavings. The shavingsthus produced not only become a cause of contamination of the cleanroom, but also adhere to the rubbing cloth thereby spoiling thesubstrate and extremely lowering the effects of the rubbing treatment.Accordingly, it is required for a masking material to have apredetermined elasticity.

It has been found by the present inventors after great deal of study onvarious high molecular materials that when a photosensitive resin havinga Rockwell hardness of M50 or more is employed, the phenomena of peelingand shaving of the film can be avoided as shown in the following Table8.

Thus, with the use of a photosensitive resin having a Rockwell hardnessof M50 or more as a masking material, it is possible to perform thepatterning of the photosensitive resin layer without spoiling theeffects of the alignment, and to obtain a precise partition of pictureelement.

13. The present inventors have found, after various experiments on thephysical properties of developer (or developing solution) and strippingagent (or stripping solution) which do not dissolve in any extent analignment film comprising polyimide, and do not give any bad influenceto the alignment film, that an organic solution having a boiling pointof not more than 130° C., in particular an alkaline solution has beenfound to be useful as it does not badly affect the alignment of a liquidcrystal or the performance of the cell.

By contrast, when an organic solution having a boiling point exceeding130° C. is employed as a developer or as a stripping agent, thedeveloper or the stripping agent which is sticked on the surface of thealignment film hardly evaporates, thus covering the surface of thealignment film, and becomes an impurity left remained within the liquidcrystal cell, thereby deteriorating the performance of the liquidcrystal cell, in particular lowering the voltage retention constant.

When an organic solution having a boiling point of not more than 130°C., preferably not more than 120° C. is employed as a developer and/oras a stripping agent, the organic solution is left remained in a verylittle amount within the alignment film comprising polyimide, and thislittle amount of the organic solution functions to increase the pretiltangle of the liquid crystal molecule. As a result, the speed of responseis improved, i.e. unexpected effects has been admitted.

It is preferable in this case to use a developer having a hydrogen ionconcentration of 10⁻¹¹.5 or more, i.e. 11.5 or less in pH.

As shown in FIG. 10, when a strong alkaline developing solution morethan 11.5 in pH is employed, the polyimide alignment film would bealkali-hydrolyzed. As a result, the remaining DC component during theoperation of a liquid crystal device is left as an electrical charge inthe film to cause an alteration of electric voltage applied to theliquid crystal, thereby inviting the lowering of contrast or thegeneration of flicker.

Since pH is influenced by carbon dioxide in air, it is advisable inproducing a developing solution 11.5 in pH to prepare a developer havingan acid dissociation constant of 10.1 or less and to make it into anaqueous solution.

14. The present inventors have conducted an experiment wherein apolyimide substrate treated in advance with rubbing was immersed intovarious organic solutions to be employed for a rinsing solution or astripping solution, and then assembled into a liquid crystal cell,thereby to investigate the performances of the liquid crystal cell. As aresult, it has been found that there is a relationship between thesolubility parameter of an organic solvent and the pretilt angle asshown in

FIG. 11. It would be clear from FIG. 11 that when the solubilityparameter is in the range of 8.7 to 10.0 cal^(1/2) ·cm^(-3/2), thepretilt angle of the liquid crystal molecule is lowered. This phenomenoncan be explained as that since the solubility parameter of the organicsolvent is very close to that of polyimide, the surface of polyimidetreated in advance with rubbing is dissolved or swelled, therebychanging the status of polyimide (unevenness or orientation degree ofmolecule). Accordingly, it is preferable to employ a solvent having thesolubility parameter of less than 8.7, preferably less than 7.0cal^(1/2) ·cm^(-3/2), or over 10.0 cal^(1/2) ·cm^(-3/2), a developer, astripping agent, and a rinsing agent. By using a solvent having thisrange of solubility parameter, any change in pretilt angle due to thepenetration of a solvent can be avoided, and the generation of edgereverse can be minimized.

As a display system using the liquid crystal device of this invention,all of the display systems in which the angle of visibility isrestricted by the difference in direction from the rising direction ofthe liquid crystal molecule under an electric field-induced state, suchas twisted nematic display, STN, SBE, and ECB can be applicable.

It is also possible to incorporate an active switch element such as TFTinto the liquid crystal display device of this invention so as to obtainan excellent display.

FIG. 12 represents a sectional view of 90° TN type liquid crystaldisplay device according to one embodiment of this invention.

In FIG. 12, a pair of transparent electrodes 2a and 2b are formedrespectively on a pair of transparent substrates 1a and 1b disposed faceto face. On these transparent electrodes 2a and 2b are formed a pair ofalignment films 3a and 3b respectively. A liquid crystal 4 is filled ina space between the pair of alignment films 3a and 3b. The liquidcrystal molecules of the liquid crystal 4 are aligned in such a mannerthat they are twisted by 90° from the state on the surface of thealignment film 3a, which is in parallel with the surface of the drawingto the state on the surface of the alignment film 3b, which isperpendicular to the surface of the drawing.

FIGS. 13A to FIG. 13E are sectional views indicating the steps ofalignment treatment of the substrate of the liquid crystal displaydevice according to this invention. In these FIGS. the alignmenttreatment only one of the substrates, i.e. the substrate 1a is shown.However, the same process as indicated in these FIGS. can also beapplied to the other substrate 1b.

As shown in FIG. 13A, the transparent electrode 2a and the alignmentfilm 3a are formed on the surface of the glass substrate 1a, and then afirst rubbing treatment in the direction of the arrow is performed onthe entire surface of the alignment film 3a. Thereafter, a photoresist 5is coated all over the surface of the alignment film 3a as shown in FIG.13B, and then selectively irradiated with light and developed therebyforming a photoresist pattern 5a as shown in FIG. 13C.

Subsequently, a second rubbing treatment in a direction which differs by180° from that of the first rubbing treatment, i.e. in the oppositedirection to that of the first rubbing treatment is performed. Then thephotoresist pattern 5a is stripped off, thereby obtaining, as shown inFIG. 13E, a liquid crystal substrate having in one picture element aplurality of regions, each of which differs by 180° in alignmentdirection from the other region.

This invention will be further explained with reference to the followingexamples and comparative examples thereby showing in detail the effectsof this invention.

In the following Examples 1 and 2, polyimide having a glass transitionpoint of 300° to 400° C. was employed as an alignment film material, anda negative photoresist was employed as a masking material.

EXAMPLE 1

A thermal ring-closure type polyimide having a glass transitiontemperature of 400° C. was coated over the surface of each oftransparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) of 10000 Å in thickness on the surface of the alignment film, ahalf of the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was performed to the exposed alignment film, andthen the layer of the mask was removed by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the second rubbing treatment portions thereof to each other.Then, Np (nametic phase) liquid crystal was filled in the space betweenthe pair of the substrates, thereby forming a liquid crystal displaycell having an inter-electrode distance of 6 μm. The liquid crystaldisplay cell thus obtained showed an excellent alignment state at theinitial state, and at the same time indicated an excellent display whichwas free from inversion of brightness and darkness according to thedifference in viewing angle in the half tone display.

EXAMPLE 2

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a glasstransition temperature of 380° C. was coated over the surface of each oftransparent substrates. Each of the substrate was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdiscrination line.

In the following Examples 3 and 4, polyimide having a glass transitionpoint of 300° to 400° C. was employed as an alignment film material, anda positive photoresist was employed as a masking material.

EXAMPLE 3

The process of Example 1 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay.

EXAMPLE 4

The process of Example 2 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and dimethylethanol amine (1.5% by weight) was used as adeveloping liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt discrination line.

Comparative Example 1

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrode of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a glasstransition temperature of 250° C. was coated over the surface of each oftransparent substrates. Each of the substrates post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, but aconspicuous deterioration in alignment was admitted after 50 hours oflife test at a temperature of 100° C.

Comparative Example 2

A whole aromatic ring-closure type polyimide having a glass transitiontemperature of 420° C. was coated over the surface of each oftransparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

In the following Examples 5 to 8, polyimide having no two-revolutionsymmetric axis in its skeleton was employed as an alignment filmmaterial, and a negative photoresist was employed as a masking material.

EXAMPLE 5

A thermal ring-closure type polyimide represented by the followinggeneral formula (11) was coated over the surface of each of transparentsubstrates, each being provided in advance with a transparent electrode.This polyimide had no two-revolution symmetrical axis in its skeleton.##STR8##

Each of the substrates was post-baked at a temperature of 280° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. In thismanufacturing process, the alignment film was not dissolved into thesolvent for the developing liquid, and found after an oblique lightingtest as being normal.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 6

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having the followinggeneral formula (12) was coated over the surface of each of transparentsubstrates. This polyimide contained no two-revolution symmetrical axisin its skeleton. ##STR9##

Each of the substrates was post-baked at a temperature of 180° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdiscrination line.

EXAMPLE 7

A solvent-soluble ring-closure type polyimide having the followinggeneral formula (13) was coated over the surface of a pair of the sametransparent substrate as that used in Example 4, and the same processesas those of Example 4 were repeated. The liquid crystal display cellthus obtained showed an excellent alignment state at the initial state,and at the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line. ##STR10##

EXAMPLE 8

A solvent-soluble ring-closure type polyimide having the followinggeneral formula (14) was coated over the surface of a pair of the sametransparent substrate as that used in Example 2, and the same processesas those of Example 2 were repeated. The liquid crystal display cellthus obtained showed an excellent alignment state at the initial state,and at the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdiscrination line. ##STR11##

In the following Examples 9 to 12, polyimide having no two-revolutionsymmetric axis in its skeleton was employed as an alignment filmmaterial, and a positive photoresist was employed as a masking material.

EXAMPLE 9

The process of Example 5 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay.

EXAMPLE 10

The process of Example 6 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and dimethylethanol amine (0.5% by weight) was used as adeveloping liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

EXAMPLE 11

The process of Example 7 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu CO. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

EXAMPLE 12

The process of Example 8 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

Comparative Example 3

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having the followinggeneral formula (15) was coated over the surface of each of transparentsubstrates. ##STR12##

Each of the substrates was post-baked at a temperature of 180° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

In this manufacturing process, when the display of the alignment filmwas tested by using an oblique light after the stripping process, therewas admitted on the whole surface of the film a trace of the flow of thesolvent.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal is filled into the space between the pair of thesubstrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained did not show a TN alignment state at the initial state, and wasincapable of conducting a picture element partition treatment.

Comparative Example 4

The process of Comparative Example 1 was repeated except that asolvent-soluble ring closure type polyimide as shown in the followinggeneral formula (16) was coated on the same substrate as that used inthe Comparative Example 1, and the same treatments as those in theComparative Example 1 were conducted. The liquid crystal display cellthus obtained did not show a TN alignment state at the initial state,and was incapable of conducting a picture element partition treatment.##STR13##

Comparative Example 5

A whole aromatic ring-closure type polyimide having the followinggeneral formula (17) was coated over the surface of each of transparentsubstrates, each being provided in advance with a transparent electrode.This polyimide contained along the longitudinal axis thereoftwo-revolution symmetrical axis in its skeleton. The resultant devicewas post-baked at a temperature of 250° C. for one hour, thereby fixingan alignment film comprising polyimide on the surface of the substrate,and then a first rubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist. ##STR14##

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

In the following Examples 13 and 14, polyimide having non-conjugatedcarbon in its skeleton, the number of the non-conjugated carbonoccupying 10 to 60% of the total number of carbon excluding thosedirectly connected to imido group was used as an alignment filmmaterial, and a negative photoresist was employed as a masking material.

EXAMPLE 13

A thermal ring-closure type polyimide having non-conjugated carbon inits skeleton, the number of the non-conjugated carbon occupying 13.8% ofthe total number of carbon excluding those directly connected to imidogroup was coated over the surface of each of transparent substrates,each being provided in advance with a transparent electrode. Each of thesubstrates was post-baked at a temperature of 280° C. for one hour,thereby fixing an alignment film comprising polyimide on the surface ofthe substrate, and then a first rubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 14

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrode of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having 33.3% innumber of non-conjugated carbon was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

In the following Examples 15 and 16, polyimide having non-conjugatedcarbon in its skeleton, the number of the non-conjugated carbonoccupying 10 to 60% of the total number of carbon excluding thosedirectly connected to imido group was used as an alignment filmmaterial, and a positive photoresist was employed as a masking material.

EXAMPLE 15

The process of Example 13 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay.

EXAMPLE 16

The process of Example 14 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

Comparative Example 6

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having 66.7% innumber of non-conjugated carbon was coated over the surface of each oftransparent substrates. Each of the substrate was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gatewiring, a signal wiring and a supplemental capacity wiring wasirradiated with light, and developed with a predetermined developingliquid, thereby patterning the photoresist to form a mask covering ahalf of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, but aconspicuous deterioration in alignment was admitted after 50 hours oflife test at a temperature of 100° C.

Comparative Example 7

A whole aromatic ring-closure type polyimide was coated over the surfaceof each of transparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

In the following Examples 17 and 18, polyimide having a relativedielectric constant of 4 or more in the frequency of 1 kHz at 20° C. wasemployed as an alignment film material, and a negative photoresist wasemployed as a masking material.

EXAMPLE 17

A thermal ring-closure type polyimide having a relative dielectricconstant of 4 was coated over the surface of each of transparentsubstrates, each being provided in advance with a transparent electrode.Each of the substrates was post-baked at a temperature of 280° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 18

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a relativedielectric constant of 4.5 was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

In the following Examples 19 and 20, polyimide having a relativedielectric constant of 4 to 7 in the frequency of 1 kHz at 20° C. wasemployed as an alignment film material, and a positive photoresist wasemployed as a masking material.

EXAMPLE 19

The process of Example 17 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay.

EXAMPLE 20

The process of Example 18 was repeated except that an acryl positivephotoresist (ARC-1, Nihon Gosei Gomu Co. Ltd.) was employed as a maskingmaterial, and NMD-3 (0.5% by weight) was used as a developing liquid.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

Comparative Example 8

TFT switch elements were mounted on one of a pair of transparentsubstrate, and a picture element electrodes of 200 μm square and made ofa transparent electrode were formed on the line in the form of matrix.Further, a supplemental capacity wiring was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a relativedielectric constant of 7.2 was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, but aconspicuous deterioration in alignment was admitted after 50 hours oflife test at a temperature of 100° C.

Comparative Example 9

A whole aromatic ring-closure type polyimide having a relativedielectric constant of 3.5 was coated over the surface of each oftransparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

In the following Examples 21 to 30, an acryl positive photoresist wasused as a masking material.

EXAMPLE 21

A thermal ring-closure type polyimide having a glass transitiontemperature of 400° C. was coated over the surface of each oftransparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a layer 10000 Å in thickness of a positive photoresistconsisting of a mixture comprising polymethacrylate, onium salt and anacetal compound on the surface of the alignment film, then a half of theregion of one picture element was irradiated with light, and finallydeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 65 m. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 22

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a glasstransition temperature of 380° C. was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a layer 8000 Å in thickness of a positive photoresistcomprising polyacrylate, sulfonate and polyphthalaldehyde on the surfaceof the alignment film, a half of the region of one picture element, i.e.a region encircled by a gate line, a signal line and a supplementalcapacity line was irradiated with light, and developed with apredetermined developing liquid, thereby patterning the photoresist toform a mask covering a half of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

EXAMPLE 23

A thermal ring-closure type polyimide having a general formula wascoated over the surface of each of transparent substrates, each beingprovided in advance with a transparent electrode. This polyimideemployed herein did not contain two-revolution symmetric axis in itsskeleton.

Each of the substrates was post-baked at a temperature of 280° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a layer 10000 Å in thickness of a positive photoresistconsisting of a mixture comprising polymethacrylate, onium salt and anacetal compound on the surface of the alignment film, then a half of theregion of one picture element was irradiated with light, and finallydeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. In thismanufacturing process, the alignment film was not dissolved into thesolvent for the developing liquid, and found after an oblique lightingtest as being normal. The pair of the substrates thus obtained wereassembled into a 90° TN by facing the mask portions thereof to eachother, and at the same time facing the second rubbing treatment portionsthereof to each other. Then, Np liquid crystal was filled into the spacebetween the pair of the substrates, thereby forming a liquid crystaldisplay cell having an inter-electrode distance of 6 μm.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay.

EXAMPLE 24

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having the generalformula (12) described above was coated over the surface of each oftransparent substrates. This polyimide employed herein did not containtwo-revolution symmetric axis in its skeleton.

Each of the substrates was post-baked at a temperature of 180° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a layer 8000 Å in thickness of a positive photoresistcomprising a mixture of polyacrylate, onium salt and fatty ester on thesurface of the alignment film, a half of the region of one pictureelement, i.e. a region encircled by a gate line, a signal line and asupplemental capacity line was irradiated with light, and developed witha predetermined developing liquid, thereby patterning the photoresist toform a mask covering a half of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

EXAMPLE 25

The process of Example 24 was repeated except that a solvent-solublering closure type polyimide shown in the general formula (13) was usedas an alignment film.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

EXAMPLE 26

The process of Example 18 was repeated except that a solvent-solublering closure type polyimide shown in the general formula (14) wasemployed as an alignment film material.

The liquid crystal display cell thus obtained showed an excellentalignment state at the initial state, and at the same time indicated anexcellent display which was free from inversion of brightness anddarkness according to the difference in viewing angle in the half tonedisplay, and also free from a tilt disclination line.

EXAMPLE 27

A thermal ring-closure type polyimide having nonconjugated carbon in itsskeleton, the number of the non-conjugated carbon occupying 13.8% of thetotal number of carbon excluding those directly connected to imido groupwas coated over the surface of each of transparent substrates, eachbeing provided in advance with a transparent electrode. Each of thesubstrates was post-baked at a temperature of 280° C. for one hour,thereby fixing an alignment film comprising polyimide on the surface ofthe substrate, and then a first rubbing treatment was performed.

After forming a layer 10000 Å in thickness of a positive photoresistcomprising a mixture of polymethylmethacrylate, nitrobenzyl ester andmethoxymethyl melamine on the surface of the alignment film, a half ofthe region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist to form a mask covering a half of the picture element.Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid (stripper).

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 28

TFT switch elements were formed on one of a pair of transparentsubstrate, and picture element electrode of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having 33.3% innumber of non-conjugated carbon was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a layer 8000 Å in thickness of a positive photoresist onthe surface of the alignment film, a half of the region of one pictureelement, i.e. a region encircled by a gate line, a signal line and asupplemental capacity line was irradiated with light, and developed witha predetermined developing liquid (developper), thereby patterning thephotoresist to form a mask covering a half of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

EXAMPLE 29

A thermal ring-closure type polyimide having a relative dielectricconstant of 4 was coated over the surface of each of transparentsubstrates, each being provided in advance with a transparent electrode.Each of the substrates was post-baked at a temperature of 280° C. forone hour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed.

After forming a layer 10000 Å in thickness of a positive photoresistcomprising a mixture of an acryl resin, sulfonate and an acetal compoundon the surface of the alignment film, a half of the region of onepicture element was irradiated with light, and developed with apredetermined developing liquid, thereby patterning the photoresist toform a mask covering a half of the picture element. Thereafter, a secondrubbing treatment in the direction opposite to the first rubbingdirection was conducted, and then the layer of the mask was removed byusing a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display.

EXAMPLE 30

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrodes were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a relativedielectric constant of 4.5 was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

In the following Examples 31 and 32, a polyimide having an imidizationdegree of 90% or less was used as an alignment film material.

EXAMPLE 31

A glass substrate having a transparent common electrode formed thereon,and another glass substrate having a picture element electrode and a TFTdriving element formed thereon were prepared. The TFT driving elementwas connected to an ITO electrode having a picture element size of110×330 μm. A layer 1000 Å in thickness of a polyimide-precursorsolution (a polyamic acid solution, SE-3140, Nissan Kagaku Co. Ltd.) wasformed by a printing method on each of the glass substrates. Theresultant substrate was sintered in an oven at a temperature of 200° C.for 30 minutes, thereby obtaining an alignment film consisting of apolyimide having an imidization degree of 75%.

To this polyimide alignment film, a first rubbing alignment treatmentwas performed, and then a positive resist of cresol novolak type(OFPR-800, Tokyo Ohka Kogyo Co. Ltd.) was coated on the film. The layerof the positive resist was exposed to light and developed to form apatterning, thereby obtaining a stripe-shaped mask which was partitionedinto a plurality of picture elements alternately neighboring to eachother. This development treatment was conducted by immersing the resistin a 3% aqueous solution of tetramethylammonium hydroxide for 3 minutes.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed. Subsequently, a pair of the substrates thus obtained wereassembled and sealed with a sealing agent in such a manner that each ofthe aligned portions having the same times of rubbing alignmenttreatment was disposed face to face with a spacer disposed therebetween,thereby obtaining a liquid crystal cell. To this liquid crystal cell, aliquid crystal composition, ZLI-1132 (E. Merck Co. Ltd.) was filledthereby to obtain a TN type liquid crystal display device.

When this liquid crystal display device was examined on the quality ofalignment of the liquid crystal, the realization of uniform alignment of90° twist was confirmed. Further, when this liquid crystal displaydevice was activated, it was possible to show a uniform display of highquality from every direction.

Although a polyimide having an imidization of 75% was used in thisexample, it was confirmed upon examining the relationship between theimidization degree and the quality of display that if a polyimide havingan imidization degree of not more than 90% is employed, it is possibleto obtain a display of excellent quality. The reason for this may beexplained as that since the polyamic acid included in the alignment filmfunctions to raise the pretilt angle, it is possible to attain asuitable pretilt angle (2° to 10°) without being affected by the contactthereof with an alkaline developing solution.

EXAMPLE 32

A glass substrate having a transparent common electrode formed thereon,and another glass substrate having picture element electrodes and TFTdriving elements formed thereon were prepared. The TFT driving elementswere connected to an ITO electrode having a picture element size of110×330 μm. A layer 900 Å in thickness of a polyimide-precursor solution(a polyamic acid solution, SE-3140, Nissan Kagaku Co. Ltd.) was formedby a printing method on each of the glass substrates. The resultantsubstrate was sintered in an oven at a temperature of 240° C. for 50minutes, thereby obtaining an alignment film consisting of a polyimidehaving an imidization degree of 90%.

To this polyimide alignment film, a first rubbing alignment treatmentwas performed, and then a positive resist (OFPR-800, Tokyo Ohka KogyoCo. Ltd.) was coated on the film. The layer of the positive resist wasexposed to light and developed to form a patterning, thereby obtaining astripe-shaped mask which was partitioned into two picture elements.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed. Subsequently, a pair of the substrates thus obtained wereassembled and sealed with a sealing agent in such a manner that each ofthe aligned portions having the same times of rubbing alignmenttreatment was disposed face to face with a spacer disposed therebetween,thereby obtaining a liquid crystal cell. To this liquid crystal cell, aliquid crystal composition, ZLI-1695 (E. Merck Co. Ltd.,Δ=0.0625) wasfilled thereby to obtain a liquid crystal display device having athickness d=4.0 μm. Since disclination lines were generated due to thevariation in the alignment direction in one picture element, a blackmatrix was formed in this example at the portions where the disclinationlines were generated.

When this liquid crystal display device was examined on the quality ofalignment of the liquid crystal, the realization of uniform alignmentwas confirmed. Further, when this liquid crystal display device wasactivated to measure the viewing angle-dependency of the contrast, itwas possible to obtain a uniform display of high quality from everydirection. FIG. 14 shows an equi-contrast curve.

In the following Examples 33 and 34, a mask having a modulus ofelasticity in tension of 20 to 500 kgf/mm² was used.

EXAMPLE 33

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide was coated over thesurface of each of transparent substrates. Each of the substrates waspost-baked at a temperature of 180° C. for one hour, thereby fixing analignment film comprising polyimide on the surface of the substrate, andthen a first rubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement. The modulus of this photoresist mask was 100 kgf/mm².

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping/liquid. In this rubbingprocess, any of peelings and shavings were not recognized.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

EXAMPLE 34

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (AL-1051, JapanSynthetic Rubber Co. Ltd.) was coated over the surface of each of thetransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, a 4% aqueous solution of polyvinyl alcohol 95% in saponificationdegree, and 1500 in polymerization degree was coated on the surface ofthe alignment film, and the resultant coated layer was baked over a hotplate at a temperature of 120° C. for 5 minutes to form a mask layer6000 Å in thickness. After forming a negative photoresist layer (OMR-85,Tokyo Ohka Kogyo Co. Ltd.) 8000 Å in thickness on the surface of themask layer, a half of the region of one picture element, i.e. a regionencircled by a gate line, a signal line and a supplemental capacity linewas irradiated with light, and developed with an alkaline developingliquid (NMD-3, Tokyo Ohka Kogyo Co. Ltd) for 30 seconds, therebypatterning the photoresist.

Then, the mask layer was patterned by immersing the substrate into a hotwater of 65° C. for 10 seconds. The photoresist layer was removed byusing ethyl Cellosolve acetate, thereby forming a mask covering a halfof the picture element. The modulus of elasticity in tension of this PVAmask was 150 kgf/mm².

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. In this rubbingprocess, any of peelings and shavings were not recognized.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

Comparative Example 10

A thermal ring-closure type polyimide was coated over the surface ofeach of transparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a positive photoresist layer (OFPR-5000, Tokyo Ohka KogyoCo. Ltd.) 8000 Å in thickness on the surface of the alignment film, ahalf of the region of one picture element was irradiated with light, anddeveloped with an alkaline developing liquid (NMD-3, Tokyo Ohka KogyoCo. Ltd) for 30 seconds, thereby patterning the photoresist. The modulusof this photoresist was found to be 10 kgf/mm².

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. In this rubbingprocess, peelings and shavings of the film were recognized.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

EXAMPLE 35

A thermal ring-closure type polyimide was coated over the surface ofeach of transparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a positive photoresist layer (OFPR-5000, Tokyo Ohka KogyoCo. Ltd.) 8000 Å in thickness on the surface of the alignment film, ahalf of the region of one picture element was irradiated with light, anddeveloped with an alkaline developing liquid (NMD-3, Tokyo Ohka KogyoCo. Ltd) for 30 seconds, thereby patterning the photoresist, therebyforming a mask covering a half of the picture element. This resist maskwas photosensitive to a wavelength corresponding to i beam (365 nm).

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. The pair of thesubstrates thus obtained were assembled into a 90° TN by facing the maskportions thereof to each other, and at the same time facing the secondrubbing treatment portions thereof to each other. Then, Np liquidcrystal was filled into the space between the pair of the substrates,thereby forming a liquid crystal display cell having an inter-electrodedistance of 6 μm. The liquid crystal display cell thus obtained showedan excellent alignment state at the initial state, and at the same timeindicated an excellent display which was free from inversion ofbrightness and darkness according to the difference in viewing angle inthe half tone display.

EXAMPLE 36

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide having a glasstransition temperature of 380° C. was coated over the surface of each oftransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 8000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element, i.e. a region encircled by a gateline, a signal line and a supplemental capacity line was irradiated withlight, and developed with a predetermined developing liquid, therebypatterning the photoresist to form a mask covering a half of the pictureelement. This resist mask was photosensitive to a wavelengthcorresponding to i beam.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. The pair of thesubstrates thus obtained were assembled into a 90° TN by facing the maskportions thereof to each other, and at the same time facing the secondrubbing treatment portions thereof to each other. Then, Np liquidcrystal was filled into the space between the pair of the substrates,thereby forming a liquid crystal display cell having an inter-electrodedistance of 6 μm. The liquid crystal display cell thus obtained showedan excellent alignment state at the initial state, and at the same timeindicated an excellent display which was free from inversion ofbrightness and darkness according to the difference in viewing angle inthe half tone display, and also free from a tilt disclination line.

Comparative Example 11

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide was coated over thesurface of each of transparent substrates. Each of the substrates waspost-baked at a temperature of 180° C. for one hour, thereby fixing analignment film comprising polyimide on the surface of the substrate, andthen a first rubbing treatment was performed.

After forming a positive photoresist layer (polyfluorobutylmethacrylate) 8000 Å in thickness on the surface of the alignment film,a half of the region of one picture element, i.e. a region encircled bya gate line, a signal line and a supplemental capacity line wasirradiated with light, and developed with a predetermined developingliquid, thereby patterning the photoresist to form a mask covering ahalf of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained failed to show the TN alignment, and was incapable ofperforming, through induction of electric voltage, a display itself.

Comparative Example 12

A whole aromatic ring-closure type polyimide having a glass transitiontemperature of 420° C. was coated over the surface of each oftransparent substrates, each being provided in advance with atransparent electrode. Each of the substrates was post-baked at atemperature of 280° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

After forming a positive photoresist layer (EBR-9, Tohre Co. Ltd.) 10000Å in thickness on the surface of the alignment film, a half of theregion of one picture element was irradiated with an electron beam underan accelerated voltage of 20 kv, and developed with a predetermineddeveloping liquid, thereby patterning the photoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained failed to show the TN alignment, and was incapable ofperforming, through induction of electric voltage, a display itself.

The following Examples 38 and 39 show examples where a water-solublepolymer was employed as a masking material.

EXAMPLE 37

A thermal ring-closure type polyimide (SE-4140, Nissan Kagaku Co. Ltd.)was coated over the surface of each of transparent substrates, eachbeing provided in advance with a transparent electrode. Each of thesubstrates was post-baked at a temperature of 280° C. for one hour,thereby fixing an alignment film comprising polyimide on the surface ofthe substrate, and then a first rubbing treatment was performed. Then, a4% aqueous solution of polyvinyl alcohol 95% in saponification degree,and 1500 in polymerization degree was coated on the surface of thealignment film, and the resultant coated layer was baked over a hotplate at a temperature of 120° C. for 5 minutes to form a mask layer4000 Å in thickness.

After forming a positive photoresist layer (OFPR-5000, Tokyo Ohka KogyoCo. Ltd.) 8000 Å in thickness on the surface of the alignment film, ahalf of the region of one picture element was irradiated with light, anddeveloped with an alkaline developing liquid (NMD-3, Tokyo Ohka KogyoCo. Ltd) for 30 seconds, thereby patterning the photoresist. Then, themask layer was patterned by immersing the substrate into a hot water of65° C. for 10 seconds. The photoresist layer was removed by using ethylCellosolve acetate, thereby forming a mask covering a half of thepicture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed by using a predetermined stripping liquid. The pair of thesubstrates thus obtained were assembled into a 90° TN facing the maskportions thereof to each other, and the same time facing the secondrubbing treatment portions thereof to each other. Then, Np liquidcrystal was filled into the space between the pair of the substrates,thereby forming a liquid crystal display cell having an inter-electrodedistance of 6 μm. The liquid crystal display cell thus obtained showedan excellent alignment state at the initial state, and at the same timeindicated an excellent display which was free from inversion ofbrightness and darkness according to the difference in viewing angle inthe half tone display.

EXAMPLE 38

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (AL-1051, NihonGosei Gomu Co. Ltd) was coated over the surface of each of thetransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, a 4% aqueous solution of polyvinyl alcohol 95% in saponificationdegree, and 1500 in polymerization degree was coated on the surface ofthe alignment film, and the resultant coated layer was baked over a hotplate at a temperature of 120° C. for 5 minutes to form a mask layer6000 Å in thickness. After forming a positive photoresist layer(OFPR-5000, Tokyo Ohka Kogyo Co. Ltd.) 8000 Å in thickness on thesurface of the mask layer, a half of the region of one picture element,i.e. a region encircled by a gate line, a signal line and a supplementalcapacity line was irradiated with light, and developed with an alkalinedeveloping liquid (NMD-3, Tokyo Ohka Kogyo Co. Ltd) for 30 seconds,thereby patterning the photoresist.

Then, the mask layer was patterned by immersing the substrate into a hotwater of 65° C. for 10 seconds. The photoresist layer was removed byusing ethyl Cellosolve acetate, thereby forming a mask covering a halfof the picture element. Thereafter, a second rubbing treatment in thedirection opposite to the first rubbing direction was conducted, andthen the layer of the mask was removed by using a hot water.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

EXAMPLE 39

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (AL-1051, NihonGosei Gomu Co. Ltd) was coated over the surface of each of thetransparent substrates. Each of the substrates was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, a 4% aqueous solution of polyvinyl alcohol 95% in saponificationdegree, and 1500 in polymerization degree was coated on the surface ofthe alignment film, and the resultant coated layer was baked over a hotplate at a temperature of 120° C. for 5 minutes to form a mask layer8000 Å in thickness. After forming a negative photoresist layer (OMR-85,Tokyo Ohka Kogyo Co. Ltd.) 10000 Å in thickness on the surface of themask layer, a half of the region of one picture element, i.e. a regionencircled by a gate line, a signal line and a supplemental capacity linewas irradiated with light, and developed with a predetermined developingliquid, thereby patterning the photoresist.

Then, the PVA layer was patterned by immersing the substrate into a hotwater of 65° C. for 10 seconds, thereby forming a mask covering a halfof the picture element. Thereafter, a second rubbing treatment in thedirection opposite to the first rubbing direction was conducted, andthen the layer of the mask was removed by using a hot water of 85° C.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

Comparative Example 13

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (AL-1051, NihonGosei Gomu Co. Ltd) was coated over the surface of each of thetransparent substrates. The resultant device was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a positive photoresist layer (OFPR-5000, Tokyo OhkaKogyo Co. Ltd.) 12000 Å in thickness on the surface of the mask layer, ahalf of the region of one picture element, i.e. a region encircled by agate line, a signal line and a supplemental capacity line was irradiatedwith light, and developed with an alkaline developing liquid (NMD-3,Tokyo Ohka Kogyo Co. Ltd.) for 30 seconds, thereby patterning thephotoresist. During this the alignment film was completely dissolved bythe alkaline developing solution.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained indicated a defective alignment at the initial state due to thefall out of part of the alignment film, and at the same time wasincapable of partitioning the picture element into two regions having adifferent rising direction of the liquid crystal molecule from eachother that can be induced by the writing through electric voltage.

Comparative Example 14

A thermal ring-closure type polyimide (SE-4140, Nissan Kagaku Co. Ltd.)was coated over the surface of each of transparent substrates, eachbeing provided in advance with a transparent electrode. Each of thesubstrates was post-baked at a temperature of 280° C. for one hour,thereby fixing an alignment film comprising polyimide on the surface ofthe substrate, and then a first rubbing treatment was performed.

After forming a negative photoresist layer (OMR-85, Tokyo Ohka Kogyo Co.Ltd.) 10000 Å in thickness on the surface of the alignment film, a halfof the region of one picture element was irradiated with light, anddeveloped with a predetermined developing liquid, thereby patterning thephotoresist.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskwas removed at a temperature of 80° C. by using a predeterminedstripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed a clear trace of the pouring flow of liquid crystal atthe initial state, due to the influence from the resist-stripping liquidto the alignment film, and at the same time indicated a defectivedisplay, thereby making it impossible to partition the picture elementinto two regions having a different rising direction of the liquidcrystal molecule from each other that can be induced by the writingthrough electric voltage.

EXAMPLE 40

A glass substrate A having a transparent common electrode formedthereon, and another glass substrate B having picture element electrodesand TFT driving elements formed thereon were prepared. The TFT drivingelement was connected to an ITO electrode having a picture element sizeof 110×330 μm. A layer 1000 Å in thickness of AL-1051 (a trade name,Nihon Gohsei Gomu Co. Ltd.) which is a polyimide represented by thegeneral formula (1) and having an imidization degree of 100% was formedby a printing method on each of the glass substrates A and B. To thesesubstrates A and B, a first rubbing alignment treatment was performed insuch a manner that the liquid crystal molecules were twisted by 90° onthe polyimide alignment film. Subsequently, OMR-83 (a trade name, TokyoOhka Kogyo Co. Ltd.), i.e. a negative resist comprising a cyclizedrubber added with a bisazido compound was formed on the alignment filmof the glass substrates A and B. in such a manner as to form astripe-shaped mask which was partitioned into a plurality of pictureelements alternately neighboring to each other. Thereafter, a secondrubbing treatment in the direction opposite to the first rubbingdirection was conducted, and then the layer of the negative resist wasremoved. Subsequently, a pair of the substrates A and B thus obtainedwere assembled and sealed with a sealing agent in such a manner thateach of the aligned portions having the same times of rubbing alignmenttreatment was disposed face to face with a spacer disposed therebetween,thereby obtaining a liquid crystal cell. To this liquid crystal cell, aliquid crystal composition, ZLI-1132 (a trade name, E. Merck Co. Ltd.)was filled thereby to obtain a liquid crystal display device.

For the stripping of this negative resist, a stripping liquid containing30% by weight of alkylbenzene sulfonate was employed. Since thealignment film is consisted of a polyimide having an imidization degreeof 100%, any deterioration of the surface of the alignment film was notadmitted even though an acid solution was used as a stripping liquid.

When this liquid crystal display device was examined on the quality ofalignment of the liquid crystal, the realization of uniform alignment of90° twist was confirmed. Further, when this liquid crystal displaydevice was activated, it was possible to show a uniform display of highquality from every direction.

EXAMPLE 41

A glass substrate A having a transparent common electrode formedthereon, and another glass substrate B having picture element electrodeand TFT driving element formed thereon were prepared. The TFT drivingelement was connected to an ITO electrode having a picture element sizeof 110×330 μm. A layer 1000 Å in thickness of a polyimide representedhaving an imidization degree of 92% was formed by coating a polyamicacid solution on each of the glass substrates A and B, and sinteringthem for one hour at a temperature of 190° C.

To these substrates A and B, a first rubbing alignment treatment wasperformed in such a manner that the liquid crystal molecules weretwisted by 90° on the polyimide alignment film. Subsequently, a negativeresist of OMR-83 (a trade name, Tokyo Ohka Kogyo Co. Ltd.) was formed onthe alignment film of the glass substrates A and B. in such a manner asto form a stripe-shaped mask which was partitioned into a plurality ofpicture elements alternately neighboring to each other. Thereafter, asecond rubbing treatment in the direction opposite to the first rubbingdirection was conducted, and then the layer of the negative resist wasremoved by using the same stripping liquid as that used in Example 41.Subsequently, a pair of the substrates A and B thus obtained wereassembled and sealed with a sealing agent in such a manner that each ofthe aligned portions having the same times of rubbing alignmenttreatment was disposed face to face with a spacer disposed therebetween,thereby obtaining a liquid crystal cell. To this liquid crystal cell, aliquid crystal composition, ZLI-1132 (a trade name, E. Merck Co. Ltd.)was filled to form a layer of liquid crystal having a thickness d=4.0μm, thereby to obtain a liquid crystal display device.

Since disclination lines were generated due to the variation in thealignment direction in one picture element, a black matrix was formed inthis example at the portions where the disclination lines weregenerated.

When this liquid crystal display device was examined on the quality ofalignment of the liquid crystal, the realization of uniform alignment of90° twist was confirmed. Further, when this liquid crystal displaydevice was operated to measure the viewing angle-dependency of thecontrast, it was possible to obtain a uniform display of high qualityfrom every direction as clearly seen from the iso-contrast curve shownin FIG. 14, indicating that it is possible to obtain a liquid crystaldisplay device of uniform and high display quality.

Comparative Example 15

A glass substrate A having a transparent common electrode formedthereon, and another glass substrate B having picture element electrodesand TFT driving elements formed thereon were prepared. The TFT drivingelement was connected to an ITO electrode having a picture element sizeof 110×330 μm. A layer 1000 Å in thickness of a polyimide having animidization degree of 88% was formed by coating a polyamic acid solutionon each of the glass substrates A and B, and sintering them for 30minutes at a temperature of 170° C.

Then, a liquid crystal display device was manufactured using the sameprocess and under the same conditions as those of Example 2.

When this liquid crystal display device was examined on the quality ofalignment of the liquid crystal, it was found that the surface of thealignment film was eroded by the stripping liquid, thereby causingdisturbances of orientation of the liquid crystal. Further, when thisliquid crystal display device was operated, there were admitted thedeterioration of contrast and the degradation in quality of the display.

EXAMPLE 42

A thermal ring-closure type polyimide represented by the general formula(2) wherein R bonding a pair of imido groups is selected as beingcyclobutane radical was coated over the surface of each of transparentsubstrates, each being provided in advance with a transparent electrode.The resultant device was postbaked at a temperature of 200° C. for onehour, thereby fixing an alignment film comprising polyimide on thesurface of the substrate, and then a first rubbing treatment wasperformed. Then, after forming a negative photoresist layer 10000 Å inthickness on the surface of the film, a half of the region of onepicture element was irradiated with light, and developed with adeveloping liquid thereby forming a mask pattern covering a half of thepicture element. In this case, a 0.75% aqueous solution ofmethylpiperidine (pH:11.5, boiling point:106° C., pKa:10.08) was used.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using acetic acid-n-butyl (solubilityparameter:8.5 cal^(1/2) ·cm^(-3/2)) as a stripping liquid. As a rinsingliquid, ethanol (solubility parameter:8.5 cal^(1/2) ·cm^(-3/2)) wasused. The pair of the substrates thus obtained were assembled into a 90°TN by facing the mask portions thereof to each other, and at the sametime facing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

The thermal transformation temperature (heat resistance temperature) ofthe photoresist used in this example was 150° C., the modulus ofelasticity in tension thereof was 2.7 GPa, the modulus of elasticity inflexure thereof was 2.8 GPa, and the Rockwell hardness thereof was M85.There was not admitted problems such as peeling or shaving of thephotoresist film.

EXAMPLE 43

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrode of 200 μm square and made of atransparent electrode was formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (Optmer-AL series,Nihon Gosei Gomu Co. Ltd), which corresponds to a polyimide representedby the general formula (2) wherein R bonding a pair of imido groups iscyclopentane was coated over the surface of each of the transparentsubstrates. The resultant device was postbaked at a temperature of 180°C. for one hour, thereby fixing an alignment film comprising polyimideon the surface of the substrate, and then a first rubbing treatment wasperformed.

Then, after forming a positive photoresist layer 8000 Å in thickness onthe surface of the film, a half of the region of one picture element,i.e. a region encircled by a gate line, a signal line and a supplementalcapacity line was irradiated with light, and developed with a developingliquid thereby forming a mask pattern covering a half of the pictureelement. In this case, a 0.5% aqueous solution of trimethylamine(pH:11.4, boiling point:3° C., pKa:9.81) was used.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using cyclohexane (solubility Parameter:8.2cal^(1/2) ·cm^(-3/2)) as a stripping liquid. As a rinsing liquid,propanol (solubility Parameter:8.2 cal^(1/2) ·cm^(-3/2)) was used. Thepair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

The thermal transformation temperature (heat resistance temperature) ofthe photoresist used in this example was 140° C., the modulus ofelasticity in tension thereof was 2.0 GPa, the modulus of elasticity inflexure thereof was 2.0 GPa, and the Rockwell hardness thereof was M117.There was not admitted problems such as peeling or shaving of thephotoresist film.

EXAMPLE 44

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the line in the form of matrix.Further, a supplemental capacity wiring was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide (Optmer-AL series,Nihon Gosei Gomu Co. Ltd), which corresponds to a polyimide representedby the general formula (2) wherein R bonding a pair of imido groups iscyclopentane was coated over the surface of each of the transparentsubstrates. Each of the substrates was post-baked at a temperature of180° C. for one hour, thereby fixing an alignment film comprisingpolyimide on the surface of the substrate, and then a first rubbingtreatment was performed.

Then, after forming a positive photoresist layer 8000 Å in thickness onthe surface of the film, a half of the region of one picture element,i.e. a region encircled by a gate line, a signal line and a supplementalcapacity line was irradiated with light, and developed with a developingliquid thereby forming a mask pattern covering a half of the pictureelement. In this case, a 0.5% aqueous solution of trimethylamine(pH:11.4, boiling point:3° C., pKa:9.81) was used.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using cyclohexane (solubility parameter:8.2cal^(1/2) ·cm^(-3/2)) as a stripping liquid. As a rinsing liquid,propanol (solubility parameter:8.2 cal^(1/2) ·cm^(-3/2)) was used. Thepair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 65 m. The liquid crystal display cell thusobtained showed an excellent alignment state at the initial state, andat the same time indicated an excellent display which was free frominversion of brightness and darkness according to the difference inviewing angle in the half tone display, and also free from a tiltdisclination line.

The thermal transformation temperature (heat resistance temperature) ofthe photoresist used in this example was 140° C., the modulus ofelasticity in tension thereof was 2.0 GPa, the modulus of elasticity inflexure thereof was 2.0 GPa, and the Rockwell hardness thereof was M117.Problems such as peeling or shaving of the photoresist film were notadmitted.

Comparative Example 16

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a solvent-soluble ring-closure type polyimide, which correspondsto a polyimide represented by the general formula (2) wherein R bondinga pair of imido groups is --CO-- was coated over the surface of each ofthe transparent substrates. The resultant device was post-baked at atemperature of 180° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a positive photoresist layer 8000 Å in thickness onthe surface of the film, a half of the region of one picture element,i.e. a region encircled by a gate line, a signal line and a supplementalcapacity line was irradiated with light, and developed with a developingliquid thereby forming a mask pattern covering a half of the pictureelement.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using a stripping liquid. The pair of thesubstrates thus obtained were assembled into a 90° TN by facing the maskportions thereof to each other, and at the same time facing the secondrubbing treatment portions thereof to each other. Then, Np liquidcrystal was filled into the space between the pair of the substrates,thereby forming a liquid crystal display cell having an inter-electrodedistance of 6 μm. The liquid crystal display cell thus obtained showedan excellent alignment state at the initial state, but a conspicuousdeterioration in alignment was admitted after 50 hours of life test at atemperature of 100° C.

Comparative Example 17

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a thermal ring-closure type polyimide, which corresponds to apolyimide represented by the general formula (2) wherein R bonding apair of imido groups is --CH₂ -- was coated over the surface of each ofthe transparent substrates. Each of the substrate was postbaked at atemperature of 220° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a phenol positive photoresist layer 10000 Å inthickness on the surface of the film, a half of the region of onepicture element was irradiated with light, and developed with adeveloping liquid thereby forming a mask pattern covering a half of thepicture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using a stripping liquid at a temperature of 80°C. The pair of the substrates thus obtained were assembled into a 90° TNby facing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm.

The liquid crystal display cell thus obtained showed a clear trace ofthe pouring flow of liquid crystal at the initial state, due to theinfluence from the resist-stripping liquid to the alignment film, aswell as due to the problem of re-adhering of the shaved dust of theresist, and at the same time indicated a defective display, therebymaking it impossible to partition the picture element into two regionshaving a different rising direction of the liquid crystal molecule fromeach other that can be induced by the writing through electric voltage.

The thermal transformation temperature (heat resistance temperature) ofthe photoresist used in this comparative example was 45° C., the modulusof elasticity in tension thereof was 0.4 GPa, the modulus of elasticityin flexure thereof was 0,8 GPa, and the Rockwell hardness thereof wasM45. There were admitted problems such as shavings of the photoresistfilm.

Comparative Example 18

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrodes were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a thermal ring-closure type polyimide, which corresponds to apolyimide represented by the general formula (2) wherein R bonding apair of imido groups is cyclopentane was coated over the surface of eachof the transparent substrates. Each of the substrates was post-baked ata temperature of 200° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a negative photoresist layer 10000 Å in thickness onthe surface of the film, a half of the region of one picture element wasirradiated with light, and developed with a developing liquid therebyforming a mask pattern covering a half of the picture element. In thiscase, a 0.07% aqueous solution of tetramethylammonium hydroxide(pH:11.9, boiling point:200° C. or more, pKa:11.9) was used.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using acetic acid n-butyl (solubilityparameter:8.5 cal^(1/2) ·cm^(-3/2)) as a stripping liquid.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an electric retention ratio of 80% at the portion ofalignment film (a region where the rubbing was conducted twice) to whichthe developing liquid was contacted, indicating a lowering of electricretention property of alignment film, and also the generation of flickerafter 100 hours of switch on, indicating a defective display.

Comparative Example 19

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a thermal ring-closure type polyimide, which corresponds to apolyimide represented by the general formula (2) wherein R bonding apair of imido groups is cyclopentane was coated over the surface of eachof the transparent substrates. Each of the substrates was post-baked ata temperature of 200° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a negative photoresist layer 10000 Å in thickness onthe surface of the film, a half of the region of one picture element wasirradiated with light, and developed with a developing liquid therebyforming a mask pattern covering a half of the picture element. In thiscase, a 1.5% aqueous solution of dimethylethanol amine (pH:13, boilingpoint:134° C.) was used.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using acetic acid n-butyl (solubilityparameter:8.5 cal^(1/2) ·cm^(-3/2)) as a stripping liquid. As a rinsingliquid, ethanol (solubility parameter:12.7 cal^(1/2) ·cm^(-3/2)) wasused.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained showed an electric retention ratio of 85% at the portion ofalignment film (a region where the rubbing was conducted twice) to whichthe developing liquid was contacted, indicating a lowering of electricretention property of alignment film, and also the generation of flickerafter 500 hours of switch on, indicating a defective display.

Comparative Example 20

TFT switch elements were mounted on one of a pair of transparentsubstrate, and picture element electrodes of 200 μm square and made of atransparent electrode were formed on the wiring in the form of matrix.Further, a supplemental capacity line was formed at the center of thepicture element. Meanwhile, on all over the surface of the other one ofthe substrates was formed a black matrix so as to correspond to thetransparent electrode and to the wiring.

Then, a thermal ring-closure type polyimide, which corresponds to apolyimide represented by the general formula (2) wherein R bonding apair of imido groups is cyclopentane was coated over the surface of eachof the transparent substrates. Each of the substrates was post-baked ata temperature of 200° C. for one hour, thereby fixing an alignment filmcomprising polyimide on the surface of the substrate, and then a firstrubbing treatment was performed.

Then, after forming a negative photoresist layer 10000 Å in thickness onthe surface of the film, a half of the region of one picture element wasirradiated with light, and developed with a developing liquid therebyforming a mask pattern covering a half of the picture element.

Thereafter, a second rubbing treatment in the direction opposite to thefirst rubbing direction was conducted, and then the layer of the maskpattern was removed by using ethylene glycolmonoethyl acetate(solubility parameter:8.7 cal^(1/2) ·cm^(-3/2)) as a stripping liquid.As a rinsing liquid for the stripping liquid, acetone was used.

The pair of the substrates thus obtained were assembled into a 90° TN byfacing the mask portions thereof to each other, and at the same timefacing the second rubbing treatment portions thereof to each other.Then, Np liquid crystal was filled into the space between the pair ofthe substrates, thereby forming a liquid crystal display cell having aninter-electrode distance of 6 μm. The liquid crystal display cell thusobtained was low in pretilt angle, causing an edge reverse, and poor incontrast.

As explained above, it has become possible to obtain a liquid crystaldisplay device which is wide in effective visible angle and excellent indisplay quality.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details, representative devices, andillustrated examples shown and described herein. Accordingly, variousmodifications may be made without departing from the spirit or scope ofthe general inventive concept as defined by the appended claims andtheir equivalents.

What is claimed is:
 1. A liquid crystal display device comprising:a pairof substrates arranged face to face with each other, each having analignment film, the alignment films facing each other; and a liquidcrystal composition filled in the space between the substrates, whereineach alignment film has a plurality of alignment regions within adisplay region, one of said alignment regions imparting a firstalignment or rise direction to liquid crystal molecules, another one ofsaid alignment regions imparting a second alignment or rise direction toliquid crystal molecules, said first alignment or rise direction beingdifferent from said second alignment or rise direction, and a differencein viewing angle within a planar direction being mutually compensated,and at least one of the alignment films comprises a polyimide having animidization degree of not less than 90%.
 2. The liquid crystal displaydevice according to claim 1, wherein said polyimide has an imidizationdegree of not less than 95%.